CN101602840A - Based on D, Biodegradable shape-memory material of L-poly(lactic acid) and preparation method thereof - Google Patents
Based on D, Biodegradable shape-memory material of L-poly(lactic acid) and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of based on D, Biodegradable shape-memory material of L-poly(lactic acid) and preparation method thereof.This shape-memory material is characterised in that, with terminal hydroxy group D, L-poly(lactic acid) (PDLLA) is soft section, the urea groups segment that forms with vulcabond and the bifunctional small molecules diamines that contains reactive hydrogen is hard section, shape memory temperature is 30-60 ℃, deformation ratio is～300% o'clock, and the fixed in shape rate is 96-100%, and the recovery of shape rate is 94-100%.It is strong that shape-memory material of the present invention has a deformation confining force, the response rate height, the good characteristic of memory good reproducibility, have biodegradability, performance controllability simultaneously, composition by telomerized polymer, can control recovery temperature near body temperature, have important use value aspect surgery Minimally Invasive Surgery and the medicine equipment implant material.
Description
Technical field
The present invention relates to a kind of based on D, the shape-memory material of L-poly(lactic acid) with and preparation method thereof, belong to field of biomedical polymer materials.
Background technology
Shape-memory material be meant can perception environmental change (temperature, light, power, electricity, magnetic) stimulation, and respond this variation, its mechanics parameter is adjusted, thereby is returned to the intelligent material that it preestablishes state.Present shape-memory material mainly contains shape memory alloy, memory pottery and memory macromolecular material three major types.Wherein, alloy and ceramic-like material with memory are found the earliest, and be most widely used.But these two kinds of materials are used at biomedical sector its limitation is arranged, higher such as the deformation recovery temperature, deformation ratio is low, can not biological degradation etc.By comparison, shapememory polymer has not only that deflection is big, easily processing, and shape response temperature is convenient to adjust, thereby is subjected to numerous research workers' attention and favor, has become the main force of present shape-memory material.
The bio-medical shape-memory material is a kind of multi-functional intelligent material, owing to be applied to human body, requires material not only to have shape memory function, and the more important thing is needs the material can biological degradation under the human body environment, and is nontoxic, harmless to human body simultaneously.Therefore Biodegradable shape-memory material is one of developing direction of intelligent shape-memory material.The more biodegradable material with memory of research mainly contains at present: poly (l-lactic acid) (PLA, ZL200410013749.6), poly-glycollide (PGA), polycaprolactone (PCL) and multipolymer (ZL200610017025.8) thereof, polyurethanes (ZL200410010734.4, ZL200610043121.X) and various matrix material (ZL200810040106.9).It is wide that wherein shape memory polyurethane has raw materials for production, and the prescription adjustability is big, and memory temperature wide ranges and adjustable and good advantages such as processing characteristics are subjected to paying close attention to widely.
Summary of the invention
The object of the present invention is to provide a kind of based on D, the Biodegradable shape-memory material of L-poly(lactic acid), this material deformation recovery temperature is beneficial to biomedical applications near body temperature.
Another object of the present invention is to provide a kind of, the preparation method of the shape-memory material of L-poly(lactic acid) based on D.
Provided by the invention based on D, the Biodegradable shape-memory material of L-poly(lactic acid) is the D by terminal hydroxy group, and L-poly(lactic acid) and vulcabond and small molecules diamine reactant form.Wherein, D, the L-poly(lactic acid) is that ammonia ester segment or the urea groups segment that soft section, vulcabond and small molecules diamines form is hard section.D wherein, soft section of L-poly(lactic acid), ammonia ester segment or urea groups segment can finally excrete by the mode of hydrolysis or enzymolysis in human body, realize the biodegradability of material with memory.
Among the present invention, D, the L-polylactic acid chain segment is a flexible chain as soft section of shape-memory material, can soften (elastic state)-solidify the transformation that changes (vitreous state) in the shape memory process at deformation temperature up and down, realizes the variation of material shape.Ammonia ester segment that vulcabond and small molecules diamines form or urea groups segment are hard section, are rigid chain segments, can form a large amount of hydrogen bonds between each hard segment molecule, serve as the effect of physical crosslinking point in whole system.
Provided by the invention based on D, the shape-memory material preparation method of L-poly(lactic acid) comprises two portions:
(1) D of terminal hydroxy group, the preparation of L-poly(lactic acid): with the stannous octoate is catalyzer, rac-Lactide and small molecules dibasic alcohol fusion ring-opening polymerization make.Polymerization temperature is 100～160 ℃, and polymerization time is 12～48 hours.Regulate the consumption of rac-Lactide and small molecules dibasic alcohol, make D, the molecular weight of L-poly(lactic acid) is between 1000～20000.
(2) preparation of material with memory: with D, after L-poly(lactic acid) and vulcabond, stannous octoate mixed by a certain percentage, reaction earlier formed the performed polymer that two ends contain isocyanic ester, 60～80 ℃ of temperature of reaction, and the reaction times is 2～6 hours; Add the bifunctional small molecules diamines that contains reactive hydrogen then, temperature of reaction is 0～10 ℃, and polymerization time is 1～4 hour, and the ratio of conditioned reaction thing can make the shape-memory material that possesses the different deformation temperature.
Among the present invention, preparation terminal hydroxy group D, in the process of L-poly(lactic acid), used small molecules dibasic alcohol is an ethylene glycol, propylene glycol, butyleneglycol or other contain the micromolecular compound of two hydroxyls.Regulate the content of small molecules dibasic alcohol and rac-Lactide, can obtain the terminal hydroxy group D of different molecular weight, the L-poly(lactic acid) can make terminal hydroxy group D, the second-order transition temperature of L-poly(lactic acid) be controlled at 10～50 ℃ with molecular weight control between 1000～20000 simultaneously.
The shape-memory material of the present invention's preparation, employed vulcabond can be selected from aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate and composition thereof.Wherein aliphatic diisocyanate can be 1,6-hexamethylene diisocyanate, isophorone diisocyanate or 4 ' 4-dicyclohexyl methane diisocyanate; Aromatic diisocyanate is 4 ' 4 diphenylmethanediisocyanates, tolylene diisocyanate or xylylene diisocyanate.
The shape-memory material of the present invention preparation, the employed bifunctional small molecules diamines that contains reactive hydrogen can be that quadrol, propylene diamine, butanediamine, hexanediamine or other contain the micromolecular compound of two amino.
The shape-memory material of the present invention's preparation, D, the L-poly(lactic acid) is 1.0: 1.1～1.0: 2.0 with the ratio of the mole dosage of vulcabond, stannous octoate and D, the ratio of the mole dosage of L-poly(lactic acid) is 0.001～0.01: 1.D, the mol ratio of L-poly(lactic acid) and small molecules diamine is 1.0: 0.1～1.0: 1.0, the mole dosage of vulcabond equals D, the mole dosage sum of small molecules diamines of L-polylactic acid diol and the bifunctional that contains reactive hydrogen.
The deformation temperature of the shape-memory material of the present invention's preparation is at 30～60 ℃, be decided by D, the molecular weight size of L-poly(lactic acid), D, the molecular weight of L-poly(lactic acid) is big more, deformation temperature is high more, deformation temperature also relies on and D, and the mol ratio of L-poly(lactic acid) and hard section is for the D of same molecular weight, the L-poly(lactic acid), multiform alternating temperature degree is high more more for hard section.
The fixed in shape rate 96～100% of the material that the present invention relates to, shape recovery ratio 94～100%.
The shape-memory material of the present invention's preparation is with D, the L-poly(lactic acid) is the material of matrix, have excellent biological compatibility and biological degradability, hard section of isocyanic ester and the formation of small molecules diamine simultaneously, constitute with amide group or urea groups, in human body, can degrade by the mode of hydrolysis or enzymolysis, and finally by organism metabolism and absorption.And can regulate its deformation temperature near body temperature, have important use value aspect surgery Minimally Invasive Surgery and the medicine equipment implant material.
Description of drawings
The shape memory demonstration graph of Fig. 1 shape-memory polymer
Embodiment
Embodiment divides two ones: first: terminal hydroxy group D, L-poly(lactic acid) synthetic; Second: shape-memory material synthetic.
First part: terminal hydroxy group D, L-poly(lactic acid) synthetic
Embodiment 1: accurately take by weighing the D of recrystallization, L-rac-Lactide 14.4g (0.1mol), butyleneglycol 0.887ml (0.01mol) and stannous octoate 0.0083g (2 * 10
-5Mol), mix, vacuum reaction, 140 ℃ were reacted 24 hours.Reactant is with chloroform dissolving, ethanol sedimentation, and vacuum-drying obtains terminal hydroxy group D to constant weight, the L-poly(lactic acid).It is 1834 that proton nmr spectra calculates molecular weight, second-order transition temperature T
g=14.27 ℃.
Embodiment 2: accurately take by weighing the D of recrystallization, L-rac-Lactide 14.4g (0.1mol), butyleneglycol 0.355ml (0.004mol) and stannous octoate 0.0083g (2 * 10
-5Mol), mix, vacuum reaction, 140 ℃ were reacted 24 hours.Reactant is with chloroform dissolving, ethanol sedimentation, and vacuum-drying obtains terminal hydroxy group D to constant weight, the L-poly(lactic acid).It is 3720 that proton nmr spectra calculates molecular weight, second-order transition temperature T
g=36.33 ℃.
Embodiment 3: accurately take by weighing the D of recrystallization, L-rac-Lactide 14.4g (0.1mol), butyleneglycol 0.177ml (0.002mol) and stannous octoate 0.0083g (2 * 10
-5Mol), mix, vacuum reaction, 140 ℃ were reacted 24 hours.Reactant is with chloroform dissolving, ethanol sedimentation, and vacuum-drying obtains terminal hydroxy group D to constant weight, the L-poly(lactic acid).It is 7434 that proton nmr spectra calculates molecular weight, second-order transition temperature T
g=45.02 ℃.
Embodiment 4: accurately take by weighing the D of recrystallization, L-rac-Lactide 14.4g (0.1mol), ethylene glycol 0.296ml (0.005mol) and stannous octoate 0.0054g (1.3 * 10
-5Mol), mix, vacuum reaction, 140 ℃ were reacted 24 hours.Reactant is with chloroform dissolving, ethanol sedimentation, and vacuum-drying obtains terminal hydroxy group D to constant weight, the L-poly(lactic acid).It is 2700 that proton nmr spectra calculates molecular weight, second-order transition temperature T
g=32.53 ℃.
Embodiment 5: accurately take by weighing the D of recrystallization, L-rac-Lactide 14.4g (0.1mol), ethylene glycol 0.059ml (0.001mol) and stannous octoate 0.0054g (1.3 * 10
-5Mol), mix, vacuum reaction, 140 ℃ were reacted 24 hours.Reactant is with chloroform dissolving, ethanol sedimentation, and vacuum-drying obtains terminal hydroxy group D to constant weight, the L-poly(lactic acid).It is 13059 that proton nmr spectra calculates molecular weight, second-order transition temperature T
g=48.96 ℃.
Second section: shape-memory material synthetic
Embodiment 6
With embodiment 1 resulting terminal hydroxy group D, L-poly(lactic acid), 1, after 6-hexamethylene diisocyanate (HDI) and stannous octoate mixed in 1.0: 1.1: 0.005 in molar ratio, add in the dry toluene, behind 75 ℃ of reaction 3h, be cooled under 10 ℃, (the butanediamine amount is 1 to add butanediamine, 6-hexamethylene diisocyanate and D, the amount of L-poly(lactic acid) poor), condition of ice bath continues reaction 2h.Product precipitates through dehydrated alcohol.Vacuum-drying obtains shape-memory material to constant weight.After tested, the second-order transition temperature of this product is 38.08 ℃, and the fixed in shape rate is 97%, and the recovery of shape rate is 98%.
Embodiment 7
With embodiment 1 resulting terminal hydroxy group D, L-poly(lactic acid), 1, after 6-hexamethylene diisocyanate (HDI) and stannous octoate mixed in 1.0: 1.4: 0.0075 in molar ratio, add in the dry toluene, behind 75 ℃ of reaction 3h, be cooled under 10 ℃, (the butanediamine amount is 1 to add butanediamine, 6-hexamethylene diisocyanate and D, the amount of L-poly(lactic acid) poor), condition of ice bath continues reaction 2h.Product precipitates through dehydrated alcohol.Vacuum-drying obtains shape-memory material to constant weight.After tested, the second-order transition temperature of this product is 45.81 ℃, and the fixed in shape rate is 98%, and the recovery of shape rate is 96%.
Embodiment 8
Adopt the response procedures of embodiment 6, but with 1,6-hexamethylene diisocyanate (HDI) changes 4 ' 4 diphenylmethanediisocyanates (MDI) into.The second-order transition temperature of products therefrom, shape memory characteristic and embodiment 6 are in the same range as.
Embodiment 9
With embodiment 2 resulting terminal hydroxy group D, L-poly(lactic acid), 1, after 6-hexamethylene diisocyanate (HDI) and stannous octoate mixed in 1.0: 1.2: 0.005 in molar ratio, add in the dry toluene, behind 75 ℃ of reaction 3h, be cooled under 10 ℃, (the quadrol amount is 1 to add quadrol, 6-hexamethylene diisocyanate and D, the amount of L-poly(lactic acid) poor), condition of ice bath continues reaction 2h.Product precipitates through dehydrated alcohol.Vacuum-drying obtains shape-memory material to constant weight.After tested, the second-order transition temperature of this product is 49.37 ℃, and the fixed in shape rate is 98%, and the recovery of shape rate is 98%.
Embodiment 10
With embodiment 2 resulting terminal hydroxy group D, L-poly(lactic acid), 1, after 6-hexamethylene diisocyanate (HDI) and stannous octoate mixed in 1.0: 1.4: 0.01 in molar ratio, add in the dry toluene, behind 75 ℃ of reaction 3h, be cooled under 10 ℃, (the quadrol amount is 1 to add quadrol, 6-hexamethylene diisocyanate and D, the amount of L-poly(lactic acid) poor), condition of ice bath continues reaction 2h.Product precipitates through dehydrated alcohol.Vacuum-drying obtains shape-memory material to constant weight.After tested, the second-order transition temperature of this product is 52.18 ℃, and the fixed in shape rate is 99%, and the recovery of shape rate is 96%
Embodiment 11
Adopt the response procedures of embodiment 9, but with 1,6-hexamethylene diisocyanate (HDI) changes 4 ' 4 diphenylmethanediisocyanates (MDI) into.The second-order transition temperature of products therefrom, shape memory characteristic and embodiment 9 are in the same range as.
Embodiment 12
With embodiment 3 resulting terminal hydroxy group D, L-poly(lactic acid), 1, after 6-hexamethylene diisocyanate (HDI) and stannous octoate mixed in 1.0: 1.1: 0.005 in molar ratio, add in the dry toluene, behind 75 ℃ of reaction 3h, be cooled under 10 ℃, (the butanediamine amount is 1 to add butanediamine, 6-hexamethylene diisocyanate and D, the amount of L-poly(lactic acid) poor), condition of ice bath continues reaction 2h.Product precipitates through dehydrated alcohol.Vacuum-drying obtains shape-memory material to constant weight.After tested, the second-order transition temperature of this product is 50.89 ℃, and the fixed in shape rate is 100%, and the recovery of shape rate is 98%.
Embodiment 13
With embodiment 3 resulting terminal hydroxy group D, L-poly(lactic acid), 1, after 6-hexamethylene diisocyanate (HDI) and stannous octoate mixed in 1.0: 1.6: 0.0075 in molar ratio, add in the dry toluene, behind 75 ℃ of reaction 3h, be cooled under 10 ℃, (the butanediamine amount is 1 to add butanediamine, 6-hexamethylene diisocyanate and D, the amount of L-poly(lactic acid) poor), condition of ice bath continues reaction 2h.Product precipitates through dehydrated alcohol.Vacuum-drying obtains shape-memory material to constant weight.After tested, the second-order transition temperature of this product is 55.37 ℃, and the fixed in shape rate is 100%, and the recovery of shape rate is 94%.
Embodiment 14
Adopt the response procedures of embodiment 13, but with 1,6-hexamethylene diisocyanate (HDI) changes tolylene diisocyanate (TDI) into.The second-order transition temperature of products therefrom, shape memory characteristic and embodiment 13 are in the same range as.
Embodiment 15
With embodiment 5 resulting terminal hydroxy group D, L-poly(lactic acid), 1, after 6-hexamethylene diisocyanate (HDI) and stannous octoate mixed in 1.0: 1.1: 0.0075 in molar ratio, add in the dry toluene, behind 75 ℃ of reaction 3h, be cooled under 10 ℃, (the quadrol amount is 1 to add quadrol, 6-hexamethylene diisocyanate and D, the amount of L-poly(lactic acid) poor), condition of ice bath continues reaction 2h.Product precipitates through dehydrated alcohol.Vacuum-drying obtains shape-memory material to constant weight.After tested, the second-order transition temperature of this product is 52.95 ℃, and the fixed in shape rate is 96%, and the recovery of shape rate is 95%.
Embodiment 16
With embodiment 5 resulting terminal hydroxy group D, L-poly(lactic acid), 1, after 6-hexamethylene diisocyanate (HDI) and stannous octoate mixed in 1.0: 1.4: 0.01 in molar ratio, add in the dry toluene, behind 75 ℃ of reaction 3h, be cooled under 10 ℃, (the quadrol amount is 1 to add quadrol, 6-hexamethylene diisocyanate and D, the amount of L-poly(lactic acid) poor), condition of ice bath continues reaction 2h.Product precipitates through dehydrated alcohol.Vacuum-drying obtains shape-memory material to constant weight.After tested, the second-order transition temperature of this product is 56.30 ℃, and the fixed in shape rate is 100%, and the recovery of shape rate is 95%.
Embodiment 17
Adopt the response procedures of embodiment 16, but with 1,6-hexamethylene diisocyanate (HDI) changes isophorone diisocyanate (IPDI) into.The second-order transition temperature of products therefrom, shape memory characteristic and embodiment 16 are in the same range as.
Fig. 1 is the shape memory demonstration graph of shape-memory polymer, and a is a circular rings among the figure, original shapes, and b-f is a shape-memory polymer deformation recovery process, and wherein, b is a temporary transient shape after the deformation, and f replys shape after the deformation.
The scope of protection of the invention is not limited to the described form of the foregoing description, and embodiment can become other forms according to the content design of invention.
Claims (6)
1, a kind of based on D, the shape-memory material of L-poly(lactic acid) is characterized in that, described material is responsive to temperature type, Biodegradable shape-memory material; It is the D with terminal hydroxy group, and the L-polylactic acid diol is soft section, and the urea groups segment that forms with vulcabond and the bifunctional small molecules diamines that contains reactive hydrogen is hard section; The D of terminal hydroxy group wherein, the molecular weight of L-polylactic acid diol is 1000～20000g/mol, second-order transition temperature is at 10～50 ℃; The shape recovery temperature of described material is at 30～60 ℃, fixed in shape rate 96～100%, shape recovery ratio 94～100%.
2, the method for preparation Biodegradable shape-memory material as claimed in claim 1, its key step is:
(1) D of terminal hydroxy group, synthesizing of L-polylactic acid diol: with the amount is D, 1/2000～1/10000 stannous octoate of L-rac-Lactide is an initiator, D, L-rac-Lactide and small molecules glycol fusion ring-opening polymerization form, and the mol ratio of reactant is D, the L-rac-Lactide: small molecules glycol=10: 1～100: 1, polymerization temperature is 100～160 ℃, and polymerization time is 12～48 hours; Wherein, the small molecules glycol is the small molecules glycol that ethylene glycol, butyleneglycol, polyoxyethylene glycol etc. contain two hydroxyls; Described D, the molecular weight of L-polylactic acid diol are 1000～20000g/mol;
(2) shape-memory material is synthetic:
The first step, the mol ratio of reactant is D, L-polylactic acid diol: vulcabond=1.0: 1.1～1.0: 2.0, with the stannous octoate is catalyzer, stannous octoate and D, the ratio of the molar weight of L-polylactic acid diol is 0.001～0.01: 1, and polymerization temperature is 60～80 ℃, and polymerization time is 2～6 hours;
In second step, adding contains the small molecules chain extension small molecules diamine of the bifunctional of reactive hydrogen, and the mol ratio of reactant is D, the L-poly(lactic acid): small molecules diamine=1.0: 0.1～1.0: 1.0, polymerization temperature are 0～10 ℃, and polymerization time is 1～4 hour.
3, preparation method according to claim 2 is characterized in that, the mole dosage of described vulcabond equals D, the mole dosage sum of small molecules diamines of L-polylactic acid diol and the bifunctional that contains reactive hydrogen.
According to claim 2 or 3 described preparation methods, it is characterized in that 4, described vulcabond is selected from aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate or its mixture.
5, preparation method according to claim 4 is characterized in that, described aliphatic diisocyanate is 1,6-hexamethylene diisocyanate, isophorone diisocyanate or 4 ' 4-dicyclohexyl methane diisocyanate; Described aromatic diisocyanate is 4 ' 4 diphenylmethanediisocyanates, tolylene diisocyanate or xylylene diisocyanate.
6, require described synthetic method according to right 2 or 3, described small molecules diamines is the micromolecular compound that quadrol, propylene diamine, butanediamine, hexanediamine, ethyl ester of lysine etc. contain two amino.
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| CN101942191A (en) * | 2010-09-15 | 2011-01-12 | 华东师范大学 | Magnetic nano compound shape memory material and preparation method thereof |
| CN102477138A (en) * | 2010-11-27 | 2012-05-30 | 中国科学院兰州化学物理研究所 | Silica cross-linking shape memory polymer material |
| CN103665299A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of poly-L-lactic acid type polyurethane shape memory material |
| WO2015018015A1 (en) * | 2013-08-08 | 2015-02-12 | 深圳市光华伟业实业有限公司 | Method for synthesis of polylactide polyol from lactide and polyol |
| CN106146777A (en) * | 2016-04-21 | 2016-11-23 | 复旦大学 | A kind of Biodegradable Shape-Memory Polyurethane material and its preparation method and application |
| CN112979912A (en) * | 2021-02-25 | 2021-06-18 | 苏州大学 | Ultra-high-toughness polylactic acid-based polyurethane urea and preparation method thereof |
| CN113980235A (en) * | 2020-07-08 | 2022-01-28 | 南京中医药大学 | Shape-adjustable oral mucosa protective tooth socket and preparation method thereof |
| CN116813867A (en) * | 2023-03-15 | 2023-09-29 | 吉林大学 | Four-arm star-shaped shape memory polyurethane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942191A (en) * | 2010-09-15 | 2011-01-12 | 华东师范大学 | Magnetic nano compound shape memory material and preparation method thereof |
| CN101942191B (en) * | 2010-09-15 | 2011-12-28 | 华东师范大学 | Magnetic nano compound shape memory material and preparation method thereof |
| CN102477138A (en) * | 2010-11-27 | 2012-05-30 | 中国科学院兰州化学物理研究所 | Silica cross-linking shape memory polymer material |
| CN102477138B (en) * | 2010-11-27 | 2013-12-11 | 中国科学院兰州化学物理研究所 | Silica cross-linking shape memory polymer material |
| CN103665299A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of poly-L-lactic acid type polyurethane shape memory material |
| WO2015018015A1 (en) * | 2013-08-08 | 2015-02-12 | 深圳市光华伟业实业有限公司 | Method for synthesis of polylactide polyol from lactide and polyol |
| CN106146777A (en) * | 2016-04-21 | 2016-11-23 | 复旦大学 | A kind of Biodegradable Shape-Memory Polyurethane material and its preparation method and application |
| CN113980235A (en) * | 2020-07-08 | 2022-01-28 | 南京中医药大学 | Shape-adjustable oral mucosa protective tooth socket and preparation method thereof |
| CN112979912A (en) * | 2021-02-25 | 2021-06-18 | 苏州大学 | Ultra-high-toughness polylactic acid-based polyurethane urea and preparation method thereof |
| CN112979912B (en) * | 2021-02-25 | 2022-07-12 | 苏州大学 | Ultra-high-toughness polylactic acid-based polyurethane urea and preparation method thereof |
| CN116813867A (en) * | 2023-03-15 | 2023-09-29 | 吉林大学 | Four-arm star-shaped shape memory polyurethane and preparation method thereof |
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